Defect engineered ternary metal spinel-type Ni-Fe-Co oxide as bifunctional electrocatalyst for overall electrochemical water splitting.

Transition metal spinel oxides were engineered with active elements as bifunctional water splitting electrocatalysts to deliver superior intrinsic activity, stability, and improved conductivity to support green hydrogen production. In this study, we reported the ternary metal Ni-Fe-Co spinel oxide electrocatalysts prepared by defect engineering strategy with rich and deficient Na+ ions, termed NFCO-Na and NFCO, which suggest the formation of defects with Na+ forming tensile strain. The Na-rich NiFeCoO4 spinel oxide reveals lattice expansion, resulting in the formation of a defective crystal structure, suggesting higher electrocatalytic active sites. The spherical NFCO-Na electrocatalysts exhibit lower OER and HER overpotentials of 248 mV and 153 mV at 10 mA cm-2 and smaller Tafel slope values of about 78 mV dec-1 and 129 mV dec-1, respectively. Notably, the bifunctional NFCO-Na electrocatalyst requires a minimum cell voltage of about 1.67 V to drive a current density of 10 mA cm-2. The present work highlights the significant electrochemical activity of defect-engineered ternary metal oxides, which can be further upgraded as highly active electrocatalysts for water splitting applications.

Structurally engineered highly efficient electrocatalytic performance of 3-dimensional Mo/Ni chalcogenides for boosting overall water splitting performance.

Hydrogen production from water splitting combined with renewable electricity can provide a viable solution to the energy crisis. A novel MoS2/NiS2/Ni3S4 heterostructure is designed as a bifunctional electrocatalyst by facile hydrothermal method to demonstrate excellent electrocatalytic performance towards overall water splitting applications. MoS2/NiS2/Ni3S4 heterostructure necessitates a low overpotential of 81 mV and 210 mV to attain a current density of 10 mA cm-2 during the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Consequently, the MoS2/NiS2/Ni3S4 heterostructure-based electrolyzer shows a low cell voltage of 1.54 V at 10 mA cm-2. The present work highlights the significance of the heterostructure configuration of transition metal sulfide-based electrocatalysts for electrochemical overall water splitting applications.

Roles of Heterojunction and Cu Vacancies in the Au@Cu2-xSe for the Enhancement of Electrochemical Nitrogen Reduction Performance.

The utilization of hydrogen (H2) as a fuel source is hindered by the limited infrastructure and storage requirements. In contrast, ammonia (NH3) offers a promising solution as a hydrogen carrier due to its high energy density, liquid storage capacity, low cost, and sustainable manufacturing. NH3 has garnered significant attention as a key component in the development of next-generation refueling stations, aligning with the goal of a carbon-free economy. The electrochemical nitrogen reduction reaction (ENRR) enables the production of NH3 from nitrogen (N2) under ambient conditions. However, the low efficiency of the ENRR is limited by challenges such as the electron-stealing hydrogen evolution reaction (HER) and the breaking of the stable N2 triple bond. To address these limitations and enhance ENRR performance, we prepared Au@Cu2-xSe electrocatalysts with a core@shell structure using a seed-mediated growth method and a facile hot-injection method. The catalytic activity was evaluated using both an aqueous electrolyte of KOH solution and a nonaqueous electrolyte consisting of tetrahydrofuran (THF) solvent with lithium perchlorate and ethanol as proton donors. ENRR in both aqueous and nonaqueous electrolytes was facilitated by the synergistic interaction between Au and Cu2-xSe (copper selenide), forming an Ohmic junction between the metal and p-type semiconductor that effectively suppressed the HER. Furthermore, in nonaqueous conditions, the Cu vacancies in the Cu2-xSe layer of Au@Cu2-xSe promoted the formation of lithium nitride (Li3N), leading to improved NH3 production. The synergistic effect of Ohmic junctions and Cu vacancies in Au@Cu2-xSe led to significantly higher ammonia yield and faradaic efficiency (FE) in nonaqueous systems compared to those in aqueous conditions. The maximum NH3 yields were approximately 1.10 and 3.64 µg h-1 cm-2, with the corresponding FE of 2.24 and 67.52% for aqueous and nonaqueous electrolytes, respectively. This study demonstrates an attractive strategy for designing catalysts with increased ENRR activity by effectively engineering vacancies and heterojunctions in Cu-based electrocatalysts in both aqueous and nonaqueous media.

Synergistic effect of Polydopamine incorporated Copper electrocatalyst by dopamine oxidation for efficient hydrogen production.

Tuning the metal-support interaction in electrocatalysts has been proposed as a viable method for manipulating the electronic structure and catalytic activity. In this work, inspired by natural hydrogenase enzyme, electrocatalysts with a hybrid metal-matrix complex using polydopamine (PDA) as a supporting matrix were synthesized for efficient green hydrogen production. Among the various Metal-PDA electrocatalysts, Cu-PDA shows outstanding catalytic activity (low overpotential (ƞ) of 104 mV at 10 mA cm-2 and small Tafel slope of 60.67 mV dec-1) with high stability at neutral pH. Also, the electrochemical impedance spectroscopy analysis verified the fast charge transfer properties of Cu-PDA (2.8 Ω cm2) than PDA (26 Ω cm2), indicating a faster proton-coupled electron transfer process in Cu-PDA electrocatalyst. Therefore, emerging nature inspired organic ligand-transition metal ion complexes can be extensively encouraged as a prospective HER electrocatalyst under neutral conditions.

Promoting electrochemical ammonia synthesis by synergized performances of Mo2C-Mo2N heterostructure.

Hydrogen has become an indispensable aspect of sustainable energy resources due to depleting fossil fuels and increasing pollution. Since hydrogen storage and transport is a major hindrance to expanding its applicability, green ammonia produced by electrochemical method is sourced as an efficient hydrogen carrier. Several heterostructured electrocatalysts are designed to achieve significantly higher electrocatalytic nitrogen reduction (NRR) activity for electrochemical ammonia production. In this study, we controlled the nitrogen reduction performances of Mo2C-Mo2N heterostructure electrocatalyst prepared by a simple one pot synthesis method. The prepared Mo2C-Mo2N0.92 heterostructure nanocomposites show clear phase formation for Mo2C and Mo2N0.92, respectively. The prepared Mo2C-Mo2N0.92 electrocatalysts deliver a maximum ammonia yield of about 9.6 µg h-1 cm-2 and a Faradaic efficiency (FE) of about 10.15%. The study reveals the improved nitrogen reduction performances of Mo2C-Mo2N0.92 electrocatalysts due to the combined activity of the Mo2C and Mo2N0.92 phases. In addition, the ammonia production from Mo2C-Mo2N0.92 electrocatalysts is intended by the associative nitrogen reduction mechanism on Mo2C phase and by Mars-van-Krevelen mechanism on Mo2N0.92 phase, respectively. This study suggests the importance of precisely tuning the electrocatalyst by heterostructure strategy to substantially achieve higher nitrogen reduction electrocatalytic activity.

Manipulating wettability of catalytic surface for improving ammonia production from electrochemical nitrogen reduction.

An electrochemical nitrogen reduction reaction (ENRR) is considered a promising alternative for the traditional Haber-Bosch process. In this study, we present a method for improving the ENRR by controlling the wettability of the catalyst surface, suppressing the hydrogen evolution reaction (HER) while facilitating N2 adsorption. Reduced-graphene oxide (rGO) with a hydrophobic surface property and a contact angle (C.A.) of 59° was synthesized through a high-density atmospheric plasma deposition. Two other hydrophilic and superhydrophobic surfaces with a C.A. of 15° and 150° were developed through additional argon plasma and heat treatment of as-deposited rGO, respectively. The ENRR results showed that the ammonia yield and Faradaic efficiency tended to increase with increasing hydrophobicity. Electrochemical measurements reveal that superhydrophobic rGO achieves a higher Faradaic efficiency (5.73 %) at -0.1 V (vs RHE) and a higher NH3 yield (9.77 µg h-1 cm-2) at -0.4 V (vs RHE) in a 0.1 M KOH electrolyte. In addition, the computational fluid dynamics simulation confirmed that the amount of time the N2 gas remains on the surface could increase by improving the hydrophobicity of the catalytic surface. This study inspires the development of the rGO electrocatalyst through surface wettability modification for boosting ammonia electrosynthesis.

Synergistic Interaction of MoS2 Nanoflakes on La2Zr2O7 Nanofibers for Improving Photoelectrochemical Nitrogen Reduction.

Ammonia is a suitable hydrogen carrier with each molecule accounting for up to 17.65% of hydrogen by mass. Among various potential ammonia production methods, we adopt the photoelectrochemical (PEC) technique, which uses solar energy as well as electricity to efficiently synthesize ammonia under ambient conditions. In this article, we report MoS2@La2Zr2O7 heterostructures designed by incorporating two-dimensional (2D)-MoS2 nanoflakes on La2Zr2O7 nanofibers (MoS2@LZO) as photoelectrocatalysts. The MoS2@LZO heterostructures are synthesized by a facile hydrothermal route with electrospun La2Zr2O7 nanofibers and Mo precursors. The MoS2@LZO heterostructures work synergistically to amend the drawbacks of the individual MoS2 electrocatalysts. In addition, the harmonious activity of the mixed phase of pyrochlore/defect fluorite-structured La2Zr2O7 nanofibers generates an interface that aids in increased electrocatalytic activity by enriching oxygen vacancies in the system. The MoS2@LZO electrocatalyst exhibits an enhanced Faradaic efficiency and ammonia yield of approximately 2.25% and 10.4 µg h-1 cm-2, respectively, compared to their corresponding pristine samples. Therefore, the mechanism of improving the PEC ammonia production performance by coupling oxygen-vacant sites to the 2D-semiconductor-based electrocatalysts has been achieved. This work provides a facile strategy to improve the activity of PEC catalysts by designing an efficient heterostructure interface for PEC applications.

In Situ Grown CoMn2 O4 3D-Tetragons on Carbon Cloth: Flexible Electrodes for Efficient Rechargeable Zinc-Air Battery Powered Water Splitting Systems.

The integration of energy conversion and storage systems such as electrochemical water splitting (EWS) and rechargeable zinc-air battery (ZAB) is on the vision to provide a sustainable future with green energy resources. Herein, a unique strategy for decorating 3D tetragonal CoMn2 O4 on carbon cloth (CMO-U@CC) via a facile one-pot in situ hydrothermal process, is reported. The highly exposed morphology of 3D tetragons enhances the electrocatalytic activity of CMO-U@CC. This is the first demonstration of such a bifunctional activity of CMO-U@CC in an EWS system; it achieves a nominal cell voltage of 1.610 V @ 10 mA cm-2 . Similarly, the fabricated rechargeable ZAB delivers a specific capacity of 641.6 mAh gzn -1 , a power density of 135 mW cm-2 , and excellent cyclic stability (50 h @ 10 mA cm-2 ). Additionally, a series of flexible solid-state ZABs are fabricated and employed to power the assembled CMO-U@CC-based water electrolyzer. To the best of the authors' knowledge, this is the first demonstration of an in situ-grown binder-free CMO-U@CC as a flexible multifunctional electrocatalyst for a built-in integrated rechargeable ZAB-powered EWS system.

Facile hydrothermal synthesis of carbon-coated cobalt ferrite spherical nanoparticles as a potential negative electrode for flexible supercapattery.

Battery type electrodes would replace the currently available pseudocapacitive electrodes by the cause of high energy density and long discharge time. In this regard, battery type carbon coated CoFe2O4 spherical nanoparticles is prepared by the facile hydrothermal method and tested as the possible negative electrode for supercapattery applications. The phase purity, electronic states of elements, and the presence of carbon is inferred through various sophisticated techniques. The calculated surface area of CoFe2O4 and carbon coated CoFe2O4 are found to be 9 and 26 m2 g-1, respectively. The morphological analysis confirms the formation of uniform CoFe2O4 nanospheres (∼25 nm) with a thin layer of carbon coating (∼2 nm). The amorphous carbon coating over CoFe2O4 nanosphere is identified via high-resolution transmission electron microscope. The observed peak and plateau regions in the cyclic voltammogram and galvanostatic charge/discharge curves reveals the battery-type charge storage behaviour of the material. The carbon coated CoFe2O4 delivers the maximum length capacitance of 9.9 F m-1 at 1 mV s-1 with a useful lifespan over 5000 cycles. The electrochemical impedance spectroscopy reveals that the carbon-coated CoFe2O4 delivers the low charge transfer resistance than CoFe2O4. Further, the fabricated supercapattery provides the energy density of 160 × 10-8 Wh cm-1 at a power density of 67.2 µW cm-1. As well as, the device shows 93% of coulombic efficiency and 75% of the specific capacitance retention over 11,000 cycles. Overall, it is believed that the carbon-coated CoFe2O4 can serve as a good candidate for flexible supercapatteries.